WO2008128419A1 - Cleaning composition for removing residues from plasma etch - Google Patents

Cleaning composition for removing residues from plasma etch Download PDF

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Publication number
WO2008128419A1
WO2008128419A1 PCT/CN2008/000682 CN2008000682W WO2008128419A1 WO 2008128419 A1 WO2008128419 A1 WO 2008128419A1 CN 2008000682 W CN2008000682 W CN 2008000682W WO 2008128419 A1 WO2008128419 A1 WO 2008128419A1
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WIPO (PCT)
Prior art keywords
acid
cleaning solution
solution according
citric acid
cleaning
Prior art date
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PCT/CN2008/000682
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French (fr)
Chinese (zh)
Inventor
Bing Liu
Libbert Hongxiu Peng
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Anji Microelectronics (Shanghai) Co., Ltd
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Publication of WO2008128419A1 publication Critical patent/WO2008128419A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys of copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/106—Other heavy metals refractory metals
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
    • C11D2111/22—

Definitions

  • the present invention relates to a cleaning liquid in a semiconductor manufacturing process, and in particular to a cleaning liquid for cleaning a plasma etching residue.
  • the application, exposure and imaging of the photoresist layer is a necessary process step for the pattern fabrication of the components.
  • the residue of the photoresist layer material needs to be completely removed before the next process step (i.e., after coating, imaging, ion implantation, and etching of the photoresist layer). Ion bombardment in the doping step hardens the photoresist layer polymer, thus making the photoresist layer less soluble and more difficult to remove.
  • this layer of photoresist film has been removed using a two-step process (dry ashing and wet etching).
  • the first step uses dry ashing to remove most of the photoresist layer (PR); the second step uses a corrosion inhibitor composition wet etch/clean process to remove the remaining photoresist layer.
  • the corrosion inhibitor composition can only remove residual polymer photoresist layers and inorganic materials, and cannot damage metal layers such as aluminum layers.
  • Typical cleaning solutions in the prior art are as follows: amine cleaning solution, semi-aqueous amine based (non-hydroxyl amine) cleaning solution and fluoride cleaning solution.
  • the first two types of cleaning liquids need to be used at high temperatures (generally between 60 ° C and 80 ° C), and there is a problem of large metal corrosion rate; however, existing fluoride-based cleaning liquids also have some defects, such as Corrosion of metal and non-metal substrates cannot be controlled at the same time, and the channel feature size is changed due to the large etching rate, which further leads to a change in the semiconductor structure and a relatively small cleaning operation window.
  • US 6,828,289 A cleaning solution comprising: an acidic buffer, an organic polar solvent, a fluorine-containing substance and water, and having a pH between 3 and 7, wherein the acidic buffer is composed of an organic carboxylic acid or a polybasic acid Ammonium salt group.
  • the composition ratio is between 10:1 and 1:10, but it is emphasized that it cannot contain ethylene glycol organic solvents.
  • US 5,698,503 discloses a fluorine-containing cleaning liquid which uses a large amount of ethylene glycol, which has a large viscosity and surface tension, thereby affecting the cleaning effect. No.
  • 5,972,862 discloses a fluorine-containing cleaning liquid comprising a fluorine-containing substance, a weak acid, a weak base and an organic polar solvent, having a pH of from 7 to 11, and since it does not contain a buffer system, the cleaning effect is unstable and various problems exist.
  • the inhibitors used are usually catechol and pyrogallol. These inhibitors cannot simultaneously control the etching rate of metals and oxides; they are also harmful to the environment and human health.
  • the purpose of the invention is to solve the problem that the cleaning effect of the existing ion etching residue cleaning liquid is not good or unstable, the corrosion of the substrate is large, the operation window is small, and the environment is polluted, thereby providing a strong cleaning ability.
  • the cleaning solution of the present invention contains the following components: a citric acid/citrate buffered aqueous solution, a polymeric corrosion inhibitor, a cryoprotectant, a fluoride, and a solvent.
  • the content of the citric acid/citrate buffer aqueous solution in the cleaning solution is preferably 15% to 56% by mass; and the content of the polymer corrosion inhibitor is preferably 0.0001% by mass. 10%; the content of the antifreeze agent is preferably 0.0001% to 10% by mass; The content of the fluoride is preferably 0.01% to 3% by mass; and the mass percentage of the solvent is preferably 40% to 80% by mass.
  • the citric acid/citrate buffer aqueous solution preferably has a mass percentage of citric acid and citrate of from 5% to 60%, more preferably from 10% to 50%.
  • the citrate is preferably a salt of citric acid formed with an inorganic base or a quaternary ammonium hydroxide; wherein, an inorganic base such as ammonia water and potassium hydroxide, a quaternary ammonium hydroxide such as tetramethylammonium hydroxide and Tetraethylammonium hydroxide and the like.
  • the polyfunctional citric acid/citrate buffered aqueous solution not only has a buffering function, but also has a strong chelating ability and an ability to clean inorganic residues.
  • the polymer corrosion inhibitor is preferably selected from one or more of a hydroxyl group-containing polymer and a carboxyl group-containing polymer.
  • the hydroxyl group-containing polymer is preferably a hydroxyl group-containing polyether or polyvinyl alcohol; and the carboxyl group-containing polymer is preferably a carboxyl group-containing polyether, polymaleic anhydride, polyacrylic acid, or polymethyl group.
  • the polymer corrosion inhibitor in the cleaning liquid formulation of the invention can be used as a corrosion inhibitor, a surfactant or a chelating agent, and is harmless to the environment and human body, and avoids the traditional corrosion inhibitor, such as catechol Contamination with pyrogallol, etc., and it also has a good corrosion inhibition effect on metals and non-metals.
  • the antifreeze agent may be selected from the group consisting of polyhydric alcohols such as ethylene glycol and propylene glycol in glycols, glycerol in triols, and pentaerythritol in tetrahydric alcohols.
  • polyhydric alcohols such as ethylene glycol and propylene glycol in glycols, glycerol in triols, and pentaerythritol in tetrahydric alcohols.
  • the antifreeze is preferably used in an amount of 0.0001% to 10% by mass; a smaller amount of the antifreezing agent on the surface of the cleaning liquid.
  • a preferred salt of the fluoride is hydrogen fluoride and hydrogen fluoride is formed with a base or more, such as HF, N3 ⁇ 4F, N (CH3) 4 F or N (CH 2 OH) 3 HF, etc. .
  • the base is preferably ammonia water, quaternary ammonium hydroxide or alcohol amine.
  • the solvent may be selected from one or more of sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolidinone, amide and ether.
  • the sulfoxide is preferably diethyl sulfoxide or methyl sulfoxide
  • the sulfone is preferably methyl sulfone, ethyl sulfone or sulfolane
  • the imidazolium is preferably 2-imidazolium, 1,3-dimethyl-2-imidazolium or 1,3-diethyl-2-imidazolium
  • the pyrrolidone is preferably N-methylpyrrole a ketone
  • the imidazolinone is preferably 1,3-dimethyl-2-imidazolidinone (DMI)
  • the amide is preferably dimethylformamide
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monobut
  • the cleaning solution of the present invention may further contain a small molecule inhibitor, preferably in an amount of less than or equal to 10% by mass.
  • the small molecule inhibitor may be selected from phenols such as phenol, 1,2-dihydroxyphenol, p-hydroxyphenol or pyrogallol; carboxylic acids such as benzoic acid, p-aminobenzoic acid (PABA), Phthalic acid (PA) or gallic acid (GA); carboxylic acid esters such as methyl paraben, methyl phthalate or propyl gallate; acid anhydrides such as acetic anhydride or hexanoic anhydride Et.; benzotriazoles, such as benzotriazole, methylbenzotriazole or 4-carboxybenzotriazole; phosphonic acids such as 1,3-(hydroxyethyl)-2, 4,6-triphosphonic acid (HEDPA), aminotrimethylenephosphonic acid (ATMP) or 2-phosphonic acid butyl phosphonium-1,2,4-tricarbox
  • the cleaning liquid of the present invention can be used simply by uniformly mixing the above components.
  • the cleaning solution can be used in a variety of cleaning instruments and cleaning methods such as batch immersion, batch rotary or single-chip rotary processors.
  • the cleaning solution of the invention can be used in a large temperature range, generally at room temperature
  • the reagents and starting materials used in the present invention are commercially available.
  • the medium ion etching residue has a high cleaning efficiency.
  • a multifunctional citric acid/citrate buffer aqueous solution is adopted, which not only has a buffering function, but also has a strong chelating ability, and ensures the efficiency and stability of the cleaning liquid cleaning effect.
  • the cleaning solution of the present invention has a low ratio to non-metal and metal substrates such as Si, Si0 2 , tetraethoxysilane silica (PETEOS), low dielectric materials, Ti, A1 and Cu, etc. Etching rate.
  • the cleaning liquid of the present invention can be used over a wide temperature range, and is generally used in the range of room temperature to 45 ° C, thereby avoiding the high metal corrosion rate in the prior art due to the high use temperature.
  • the polymer corrosion inhibitor used in the cleaning liquid formulation of the invention can simultaneously perform good corrosion inhibition on metals and non-metals.
  • the cleaning liquid of the present invention is safe to the environment and human body, and has no pollution hazard.
  • the cleaning solution of the invention adopts a polymer corrosion inhibitor, which has high-efficiency corrosion inhibition effect, and is also non-toxic to the environment and the human body, and avoids the use of traditional corrosion inhibitors such as catechol and pyrogallol. Pollution hazard.
  • the cleaning liquid of the invention has excellent low temperature resistance, can be stored at -18 ° C for two months without freezing, and the antifreeze has a great influence on the surface tension and solution viscosity of the cleaning liquid in its preferred dosage range. small, It does not affect the cleaning performance of the wafer, and it has no corrosive effect on the substrate. Summary of the invention
  • the content of citric acid and ammonium citrate is 5% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
  • the content of citric acid and tetramethylammonium citrate is 60% by mass, and the content ratio of citric acid to tetramethylammonium citrate is 1:1.
  • citric acid/tetraethylammonium citrate buffer the content of citric acid and tetraethylammonium citrate is 10% by mass, and the content ratio of citric acid to citric acid tetraethylene hinge is 1:30.
  • citric acid/potassium citrate buffer solution the content of citric acid and potassium citrate is 50% by mass, and the content ratio of citric acid to potassium citrate is 10:1.
  • citric acid/sodium citrate buffered water solution 3%% hydroxyl-containing polyethyl ether (molecular weight 1000), 2wt% carboxyl group-containing polyether (molecular weight 1000), 0.0001% ethylene glycol, 0.5wt% hydrogen fluoride, 0.5% fluorine Tetramethylammonium, 1% acetic anhydride and 62.9999 wt% 2-imidazolium.
  • citric acid/sodium citrate buffer the content of citric acid and sodium citrate is 20% by mass, and the ratio of citric acid to sodium citrate is 20:1.
  • citric acid/ammonium citrate buffered water solution 40wt% citric acid/ammonium citrate buffered water solution, 0.001wt% polymaleic anhydride (molecular weight 600), lwt% ethylene glycol, lwt% N(CH 2 OH) 3 HF, 1 ⁇ % hydrogen fluoride, lwt% gallic acid Ester and 55.999 wt% methyl ethyl sulfoxide.
  • the content of citric acid and ammonium citrate is 40% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
  • citric acid/ammonium citrate buffered water solution 50wt% citric acid/ammonium citrate buffered water solution, 0.01% polyacrylic acid (molecular weight 700), 0.001% by weight of ethylene glycol, 2wt% hydrogen fluoride, 5wt% methyl phthalate and 42.989wt% l, 3-dimethyl Base-2-imidazolium.
  • polyacrylic acid molecular weight 700
  • the content ratio of citric acid to ammonium citrate is 25:1.
  • the content of citric acid and ammonium citrate is 25 wt% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
  • citric acid/ammonium citrate buffered water solution 0.1%% acrylic acid copolymer with maleic acid (molecular weight 1000), 0.1wt% ethylene glycol, 0.1% hydrogen fluoride, 0.1% ammonium fluoride, 0.6wt% fluorinated four Methylammonium, 2% by weight gallic acid and 72% by weight of ethylene glycol monoethyl ether.
  • the content of citric acid and ammonium citrate is 35 wt% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
  • the content of citric acid and ammonium citrate is 45 wt% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
  • citric acid/ammonium citrate buffered water solution 2wt% styrene and maleic acid copolymer (minutes Amount 1500), 2% by weight of ethylene glycol, 1% by weight of ammonium fluoride and 5 wt% of sulfolane, 2% by weight of p-aminobenzoic acid and 48% by weight of propylene glycol monobutyl ether.
  • the content of citric acid and ammonium citrate is 5% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
  • the content of citric acid and ammonium citrate is 55 wt% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
  • citric acid/ammonium citrate buffer solution the content of citric acid and ammonium citrate is 15% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
  • citric acid/ammonium citrate buffered water solution 0.001% polyammonium methacrylate (molecular weight 1000), 0.008 ⁇ % ethylene glycol, 0.1% hydrogen fluoride, 0.891wt% p-hydroxyphenol and 69wt% l, 3- Ethyl-2-imidazolidinone.
  • the content of citric acid and ammonium citrate is 25 wt% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
  • citric acid/sodium citrate buffer the content of citric acid and sodium citrate is 10% by mass, and the content ratio of citric acid to ammonium citrate is 20:1.
  • the content of citric acid and ammonium citrate is 5% by mass, and the content ratio of citric acid to ammonium citrate is 20:1.
  • Cleaning agent 1 24.55wt% citric acid / tetramethylammonium citrate buffered water solution (22.09wt% water, 2.37wt% tetramethylammonium citrate and 0.09wt% citric acid), 0.15%% hydroxyindole polyethyl ether (molecular weight 1000), 0.3 wt% benzotriazole, 0.5% ethylene glycol, 1.5%% fluorinated hinge and 73 wt% N-methylpyrrolidone.
  • Cleaning agent 2 24.55wt% citric acid / tetraethylammonium citrate buffered aqueous solution (22.09wt% water, 2.37wt% tetraethylammonium citrate and 0.09wt% citric acid), 0.15%% hydroxyl-containing polyethyl ether ( Molecular weight 1000), 0.3wt% 4-carboxybenzotriazole, 0.5wt% ethylene glycol, 10 wt% 1, 3-dimethyl-2-imidazolidinone and 63 wt% N-methylpyrrolidone.
  • Cleaning agent 3 34.55 wt% citric acid / tetraethylammonium citrate buffered aqueous solution (31.09 wt% water, 3.33 wt% tetraethylammonium citrate and 0.13 wt% citric acid), 0.15 ⁇ /. Hydroxy-containing polyethyl ether (molecular weight L000), 0.3 wt% methylbenzotriazole, 0.5 wt% ethylene glycol, 1.5% ammonium fluoride and 63 wt% N-methylpyrrolidone.
  • the cleaning agents 1 to 3 were tested for metal and non-metal corrosion rates as follows. The test results are shown in Table 1.
  • the cleaning liquid composition of the present invention has a corrosion rate for metals (such as metal aluminum) and non-metal (such as PETEOS) used in semiconductor fabrication, which are close to or less than 2 angstroms normally required by the semiconductor industry. Every minute, it does not substantially erode the substrate.
  • metals such as metal aluminum
  • PETEOS non-metal

Abstract

A cleaning composition for removing the residues from plasma etch includes aqueous citric acid/citrate buffer solution, fluoride, macromolecule anti-corrosion, antifreezer and solvent. The cleaning composition may clean the residues from plasma etch, and has low etch rate for a nonmetal and metal substrate, such as Si, SiO2, tetraethylorthosilicate (PETEOS), low dielectric material, Ti, Al and Cu.

Description

一种清洗等离子刻蚀残留物的清洗液 技术领域  Cleaning liquid for cleaning plasma etching residues
本发明涉及半导体制造工艺中一种清洗液，具体的涉及一种清洗等离子 刻蚀残留物的清洗液。 技术背景  The present invention relates to a cleaning liquid in a semiconductor manufacturing process, and in particular to a cleaning liquid for cleaning a plasma etching residue. technical background
在半导体元器件制造过程中， 光阻层的涂敷、 曝光和成像对元器件的图 案制造来说是必要的工艺步骤。在图案化的最后（即在光阻层的涂敷、成像、 离子植入和蚀刻之后）进行下一工艺步骤之前， 光阻层材料的残留物需彻底 除去。 在掺杂步骤中离子轰击会硬化光阻层聚合物， 因此使得光阻层变得 不易溶解从而更难于除去。 至今在半导体制造工业中一般使用两步法（干法 灰化和湿蚀刻） 除去这层光阻层膜。 第一步利用干法灰化除去光阻层 （PR) 的大部分； 第二步利用缓蚀剂组合物湿蚀刻 /清洗工艺清洗去除剩余的光阻 层。在第二步的清洗工艺过程中， 缓蚀剂组合物只能除去残留的聚合物光阻 层和无机物， 而不能损害金属层如铝层。  In the fabrication of semiconductor components, the application, exposure and imaging of the photoresist layer is a necessary process step for the pattern fabrication of the components. The residue of the photoresist layer material needs to be completely removed before the next process step (i.e., after coating, imaging, ion implantation, and etching of the photoresist layer). Ion bombardment in the doping step hardens the photoresist layer polymer, thus making the photoresist layer less soluble and more difficult to remove. Up to now, in the semiconductor manufacturing industry, this layer of photoresist film has been removed using a two-step process (dry ashing and wet etching). The first step uses dry ashing to remove most of the photoresist layer (PR); the second step uses a corrosion inhibitor composition wet etch/clean process to remove the remaining photoresist layer. In the cleaning process of the second step, the corrosion inhibitor composition can only remove residual polymer photoresist layers and inorganic materials, and cannot damage metal layers such as aluminum layers.
现有技术中典型的清洗液有以下几种： 胺类清洗液， 半水性胺基（非羟 胺类）清洗液和氟化物类清洗液。 其中， 前两类清洗液需要在高温（一般在 60°C到 80°C之间）下使用， 存在金属腐蚀速率较大的问题； 而现有的氟化物 类清洗液也存在一些缺陷， 如不能同时控制金属和非金属基材的腐蚀， 因蚀 刻率较大而造成通道特征尺寸改变， 进一步导致半导体结构改变， 以及清洗 操作窗口比较小等。  Typical cleaning solutions in the prior art are as follows: amine cleaning solution, semi-aqueous amine based (non-hydroxyl amine) cleaning solution and fluoride cleaning solution. Among them, the first two types of cleaning liquids need to be used at high temperatures (generally between 60 ° C and 80 ° C), and there is a problem of large metal corrosion rate; however, existing fluoride-based cleaning liquids also have some defects, such as Corrosion of metal and non-metal substrates cannot be controlled at the same time, and the channel feature size is changed due to the large etching rate, which further leads to a change in the semiconductor structure and a relatively small cleaning operation window.
现有文献已公幵的清洗液也或多或少存在一些缺点： US 6,828,289公开 了一种清洗液， 其包括： 酸性缓冲液、 有机极性溶剂、 含氟物质和水， 且 pH 值在 3〜7之间， 其中的酸性缓冲液由有机羧酸或多元酸与所对应的铵盐组. . 成， 组成比例为 10: 1至 1 : 10之间， 但强调不能含有乙二醇类有机溶剂。 US 5 , 698, 503公开了一种含氟清洗液， 其大量使用乙二醇， 该清洗液的粘度 与表面张力都很大， 从而影响清洗效果。 US 5,972,862公开了一种含氟清洗 液， 其包括含氟物质、 弱酸、 弱碱和有机极性溶剂， pH为 7〜11， 由于其不 含有缓冲体系， 清洗效果不稳定， 存在多样的问题。 The cleaning fluids that have been published in the literature have more or less disadvantages: US 6,828,289 A cleaning solution comprising: an acidic buffer, an organic polar solvent, a fluorine-containing substance and water, and having a pH between 3 and 7, wherein the acidic buffer is composed of an organic carboxylic acid or a polybasic acid Ammonium salt group. The composition ratio is between 10:1 and 1:10, but it is emphasized that it cannot contain ethylene glycol organic solvents. US 5,698,503 discloses a fluorine-containing cleaning liquid which uses a large amount of ethylene glycol, which has a large viscosity and surface tension, thereby affecting the cleaning effect. No. 5,972,862 discloses a fluorine-containing cleaning liquid comprising a fluorine-containing substance, a weak acid, a weak base and an organic polar solvent, having a pH of from 7 to 11, and since it does not contain a buffer system, the cleaning effect is unstable and various problems exist.
现有技术中， 使用的抑制剂通常为邻苯二酚和偏苯三酚等，这些抑制剂 不能同时控制金属以及氧化物的蚀刻速率； 同时对环境和人体健康有危害。  In the prior art, the inhibitors used are usually catechol and pyrogallol. These inhibitors cannot simultaneously control the etching rate of metals and oxides; they are also harmful to the environment and human health.
因此， 寻求可避免以上现有的技术缺陷， 既具有较强的清洗能力， 又能 满足对基材的低刻蚀率，较大操作窗口和环境友好等其它清洗要求的清洗液 成为半导体制造工艺领域亟待解决的问题。 发明概要  Therefore, it is sought to avoid the above-mentioned existing technical defects, and to have a relatively high cleaning ability, and to meet the low etching rate of the substrate, a large operating window and environmentally friendly cleaning liquids, etc., become a semiconductor manufacturing process. The problem that needs to be solved in the field. Summary of invention
本发明的目的是为了解决现有离子刻蚀残留物清洗液清洗效果不佳或 不稳定， 对基材腐蚀性大， 操作窗口较小， 环境污染的问题， 而提供一种清 洗能力强， 具有低刻蚀率且安全无毒害的等离子刻蚀残留物清洗液。  The purpose of the invention is to solve the problem that the cleaning effect of the existing ion etching residue cleaning liquid is not good or unstable, the corrosion of the substrate is large, the operation window is small, and the environment is polluted, thereby providing a strong cleaning ability. A low etch rate, safe and non-toxic plasma etch residue cleaning solution.
本发明的清洗液含有下列成分：柠檬酸 /柠檬酸盐缓冲水溶液、高分子腐 蚀抑制剂、 抗冻剂、 氟化物和溶剂。  The cleaning solution of the present invention contains the following components: a citric acid/citrate buffered aqueous solution, a polymeric corrosion inhibitor, a cryoprotectant, a fluoride, and a solvent.
其中，所述的柠檬酸 /柠檬酸盐缓冲水溶液在清洗液中的含量较佳的为质 量百分比 15%〜56%； 所述的高分子腐蚀抑制剂的含量较佳的为质量百分比 0.0001%〜10%； 所述的抗冻剂的含量较佳的为质量百分比 0.0001%〜10%； 所述的氟化物的含量较佳的为质量百分比 0.01%〜3%；所述的溶剂的质量百 分比较佳的为质量百分比 40%〜80%。 Wherein, the content of the citric acid/citrate buffer aqueous solution in the cleaning solution is preferably 15% to 56% by mass; and the content of the polymer corrosion inhibitor is preferably 0.0001% by mass. 10%; the content of the antifreeze agent is preferably 0.0001% to 10% by mass; The content of the fluoride is preferably 0.01% to 3% by mass; and the mass percentage of the solvent is preferably 40% to 80% by mass.
本发明中，所述的柠檬酸 /柠檬酸盐缓冲水溶液中柠檬酸和柠檬酸盐的质 量百分比含量较佳的为 5%〜60%， 更佳的为 10%〜50%。 其中， 柠檬酸和 柠檬酸盐的比例可根据需要以任何比例进行，但须使所得最终清洗液能保持 均相。 所述的柠檬酸盐较佳的为柠檬酸与无机碱或季胺氢氧化物形成的盐； 其中， 无机碱如氨水和氢氧化钾等， 季胺氢氧化物如四甲基氢氧化铵和四乙 基氢氧化铵等。 多官能团的柠檬酸 /柠檬酸盐缓冲水溶液不仅具有缓冲功能， 还具有较强的螯合能力和清洗无机残留物的能力。  In the present invention, the citric acid/citrate buffer aqueous solution preferably has a mass percentage of citric acid and citrate of from 5% to 60%, more preferably from 10% to 50%. Among them, the ratio of citric acid to citrate can be carried out in any ratio as needed, but the resulting final cleaning solution must be kept homogeneous. The citrate is preferably a salt of citric acid formed with an inorganic base or a quaternary ammonium hydroxide; wherein, an inorganic base such as ammonia water and potassium hydroxide, a quaternary ammonium hydroxide such as tetramethylammonium hydroxide and Tetraethylammonium hydroxide and the like. The polyfunctional citric acid/citrate buffered aqueous solution not only has a buffering function, but also has a strong chelating ability and an ability to clean inorganic residues.
本发明中，所述的高分子腐蚀抑制剂较佳的选自含羟塞聚合物和含羧基 聚合物中的一种或多种。其中， 所述的含羟基聚合物较佳的为含羟基聚醚或 聚乙烯醇等； 所述的含羧基聚合物较佳的为含羧基聚醚、 聚马来酸酐、 聚丙 烯酸、 聚甲基丙烯酸、 丙烯酸与马来酸共聚物、 苯乙烯与丙烯酸共聚物、 苯 乙烯与马来酸共聚物、 丙烯腈与马来酸共聚物或上述化合物的铵盐、 钾盐或 钠盐等。 本发明的清洗液配方中的高分子腐蚀抑制剂， 可作为腐蚀抑制剂、 表面活性剂或螯合剂使用， 并且对环境和人体安全无害， 避免了传统的腐蚀 抑制剂， 如邻苯二酚和偏苯三酚等的污染， 同时其还可对金属和非金属起到 很好的腐蚀抑制作用。  In the present invention, the polymer corrosion inhibitor is preferably selected from one or more of a hydroxyl group-containing polymer and a carboxyl group-containing polymer. Wherein, the hydroxyl group-containing polymer is preferably a hydroxyl group-containing polyether or polyvinyl alcohol; and the carboxyl group-containing polymer is preferably a carboxyl group-containing polyether, polymaleic anhydride, polyacrylic acid, or polymethyl group. Acrylic acid, a copolymer of acrylic acid and maleic acid, a copolymer of styrene and acrylic acid, a copolymer of styrene and maleic acid, a copolymer of acrylonitrile and maleic acid or an ammonium salt, a potassium salt or a sodium salt of the above compound. The polymer corrosion inhibitor in the cleaning liquid formulation of the invention can be used as a corrosion inhibitor, a surfactant or a chelating agent, and is harmless to the environment and human body, and avoids the traditional corrosion inhibitor, such as catechol Contamination with pyrogallol, etc., and it also has a good corrosion inhibition effect on metals and non-metals.
本发明中，所述的抗冻剂可选自多元醇，如二元醇中的乙二醇和丙二醇， 三元醇中的丙三醇， 四元醇中的季戊四醇。 抗冻剂的使用可使得本发明的清 洗液在 -18°C的条件下存放两个月不结冰。 本发明的清洗液配方中， 抗冻剂 较佳使用量为质量百分比 0.0001%〜10%； 较少量的抗冻剂对清洗液表面张 力和溶液粘度影响都很小，不会影响对晶片的清洗功效，对基材基本无腐蚀。 本发明中，所述的氟化物较佳的为氟化氢和氟化氢与碱形成的盐中的一 种或多种， 如 HF、 N¾F、 N(CH3)4F或 N(CH2OH)3HF等。 其中， 所述的碱 较佳的为氨水、 季胺氢氧化物或醇胺。 In the present invention, the antifreeze agent may be selected from the group consisting of polyhydric alcohols such as ethylene glycol and propylene glycol in glycols, glycerol in triols, and pentaerythritol in tetrahydric alcohols. The use of the antifreeze allows the cleaning solution of the present invention to be stored at -18 ° C for two months without freezing. In the cleaning liquid formulation of the present invention, the antifreeze is preferably used in an amount of 0.0001% to 10% by mass; a smaller amount of the antifreezing agent on the surface of the cleaning liquid The effects of force and solution viscosity are small, do not affect the cleaning performance of the wafer, and are substantially non-corrosive to the substrate. In the present invention, a preferred salt of the fluoride is hydrogen fluoride and hydrogen fluoride is formed with a base or more, such as HF, N¾F, N (CH3) 4 F or N (CH 2 OH) 3 HF, etc. . Among them, the base is preferably ammonia water, quaternary ammonium hydroxide or alcohol amine.
本发明中， 所述的溶剂可选自亚砜、 砜、 咪唑烷酮、 吡咯垸酮、 咪唑啉 酮、 酰胺和醚中的一种或多种。 其中， 所述的亚砜较佳的为二乙基亚砜或甲 乙基亚砜； 所述的砜较佳的为甲基砜、 乙基砜或环丁砜； 所述的咪唑垸酮较 佳的为 2-咪唑垸酮、 1，3-二甲基 -2-咪唑垸酮或 1,3-二乙基 -2-咪唑垸酮； 所述 的吡咯垸酮较佳的为 N-甲基吡咯垸酮；所述的咪唑啉酮较佳的为 1，3-二甲基 -2-咪唑啉酮 （DMI); 所述的酰胺较佳的为二甲基甲酰胺； 所述的醚较佳的 为乙二醇单甲醚、 乙二醇单乙醚、 乙二醇单丁醚、 二乙二醇单甲醚、 二乙二 醇单乙醚、二乙二醇单丁醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单丁醚、 二丙二醇单甲醚、 二丙二醇单乙醚或二丙二醇单丁醚。  In the present invention, the solvent may be selected from one or more of sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolidinone, amide and ether. Wherein, the sulfoxide is preferably diethyl sulfoxide or methyl sulfoxide; the sulfone is preferably methyl sulfone, ethyl sulfone or sulfolane; and the imidazolium is preferably 2-imidazolium, 1,3-dimethyl-2-imidazolium or 1,3-diethyl-2-imidazolium; the pyrrolidone is preferably N-methylpyrrole a ketone; the imidazolinone is preferably 1,3-dimethyl-2-imidazolidinone (DMI); the amide is preferably dimethylformamide; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or dipropylene glycol monobutyl ether.
本发明的清洗液还可含有小分子抑制剂，其含量较佳的为小于或等于质 量百分比 10%。所述的小分子抑制剂可选自酚类， 如苯酚、 1，2-二羟基苯酚、 对羟基苯酚或连苯三酚等； 羧酸类， 如苯甲酸、 对氨基苯甲酸（PABA)、 邻 苯二甲酸 （PA) 或没食子酸 （GA) 等； 羧酸酯类， 如对氨基苯甲酸甲酯、 邻苯二甲酸甲酯或没食子酸丙酯等； 酸酐类， 如乙酸酐或己酸酐等； 苯并三 氮唑类， 如苯并三氮唑、 甲基苯并三氮唑或 4-羧基苯并三氮唑等； 膦酸类如 1,3- (羟乙基） -2，4，6-三膦酸 （HEDPA)、 氨基三亚甲基膦酸 （ATMP) 或 2- 膦酸丁垸 -1， 2， 4-三羧酸 （PBTCA) 等； 或膦酸酯类等缓蚀剂中的一种或 多种。 本发明的清洗液由上述成分简单混合均匀即可使用。该清洗液可适用于 批量浸泡式、批量旋转式或单片旋转式处理器等多种清洗仪器和清洗方式中 使用。 并且， 本发明的清洗液可在较大的温度范围内使用， 一般可在室温到The cleaning solution of the present invention may further contain a small molecule inhibitor, preferably in an amount of less than or equal to 10% by mass. The small molecule inhibitor may be selected from phenols such as phenol, 1,2-dihydroxyphenol, p-hydroxyphenol or pyrogallol; carboxylic acids such as benzoic acid, p-aminobenzoic acid (PABA), Phthalic acid (PA) or gallic acid (GA); carboxylic acid esters such as methyl paraben, methyl phthalate or propyl gallate; acid anhydrides such as acetic anhydride or hexanoic anhydride Et.; benzotriazoles, such as benzotriazole, methylbenzotriazole or 4-carboxybenzotriazole; phosphonic acids such as 1,3-(hydroxyethyl)-2, 4,6-triphosphonic acid (HEDPA), aminotrimethylenephosphonic acid (ATMP) or 2-phosphonic acid butyl phosphonium-1,2,4-tricarboxylic acid (PBTCA); or phosphonates One or more of the agents. The cleaning liquid of the present invention can be used simply by uniformly mixing the above components. The cleaning solution can be used in a variety of cleaning instruments and cleaning methods such as batch immersion, batch rotary or single-chip rotary processors. Moreover, the cleaning solution of the invention can be used in a large temperature range, generally at room temperature
45°C范围内使用。 Used in the range of 45 °C.
本发明所用试剂及原料均市售可得。  The reagents and starting materials used in the present invention are commercially available.
本发明的积极进步效果在于：  The positive effects of the present invention are:
( 1 ) 本发明的清洗液的清洗半导体制造过程中等离子刻蚀残留物具有 较高的清洗效力。 本发明清洗液配方中， 采用了多官能团的柠檬酸 /柠檬酸 盐缓冲水溶液， 其不仅具有缓冲功能， 还具有较强的螯合能力， 保证了清洗 液清洗功效的高效和稳定。  (1) Cleaning of the cleaning liquid of the present invention The medium ion etching residue has a high cleaning efficiency. In the formula of the cleaning solution of the invention, a multifunctional citric acid/citrate buffer aqueous solution is adopted, which not only has a buffering function, but also has a strong chelating ability, and ensures the efficiency and stability of the cleaning liquid cleaning effect.
(2) 本发明的清洗液对非金属和金属基材， 如 Si、 Si02、 四乙氧基硅烷 二氧化硅（PETEOS) 、 低介质材料、 Ti、 A1和 Cu等， 均具有较低的蚀刻速 率。 本发明的清洗液可在较大的温度范围内使用， 一般在室温到 45°C范围内 使用， 因此可避免现有技术中因使用温度较高而引起的较高的金属腐蚀速 率。本发明清洗液配方中采用的高分子腐蚀抑制剂能同时对金属和非金属起 到很好的腐蚀抑制作用。 (2) The cleaning solution of the present invention has a low ratio to non-metal and metal substrates such as Si, Si0 2 , tetraethoxysilane silica (PETEOS), low dielectric materials, Ti, A1 and Cu, etc. Etching rate. The cleaning liquid of the present invention can be used over a wide temperature range, and is generally used in the range of room temperature to 45 ° C, thereby avoiding the high metal corrosion rate in the prior art due to the high use temperature. The polymer corrosion inhibitor used in the cleaning liquid formulation of the invention can simultaneously perform good corrosion inhibition on metals and non-metals.
(3 ) 本发明的清洗液对环境和人体安全友好， 无污染危害。 本发明清 洗液配方中采用了高分子腐蚀抑制剂， 其具有高效腐蚀抑制作用， 同时也对 环境和人体无毒害，避免了采用邻苯二酚和偏苯三酚等传统腐蚀抑制剂所带 来的污染危害。  (3) The cleaning liquid of the present invention is safe to the environment and human body, and has no pollution hazard. The cleaning solution of the invention adopts a polymer corrosion inhibitor, which has high-efficiency corrosion inhibition effect, and is also non-toxic to the environment and the human body, and avoids the use of traditional corrosion inhibitors such as catechol and pyrogallol. Pollution hazard.
本发明的清洗液耐低温性能优，可在 -18°C的条件下存放两个月不结冰， 且抗冻剂在其较佳的用量范围内对清洗液表面张力和溶液粘度影响都很小， 不会影响对晶片的清洗功效， 对基材也基本无腐蚀作用。 发明内容 The cleaning liquid of the invention has excellent low temperature resistance, can be stored at -18 ° C for two months without freezing, and the antifreeze has a great influence on the surface tension and solution viscosity of the cleaning liquid in its preferred dosage range. small, It does not affect the cleaning performance of the wafer, and it has no corrosive effect on the substrate. Summary of the invention
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在 所述的实施例范围之中。  The invention is further illustrated by the following examples, which are not intended to limit the invention.
实施例 1 Example 1
15wt%柠檬酸 /柠檬酸铵缓冲水溶液， 0.0001 wt%含羟塞聚乙基醚 （分子 量 1000)， 5wt%乙二醇， 2wt%氟化铵和 77.9999 ％环丁砜。  15 wt% citric acid / ammonium citrate buffered water solution, 0.0001 wt% hydroxy-containing polyethyl ether (molecular weight 1000), 5 wt% ethylene glycol, 2 wt% ammonium fluoride and 77.9999 % sulfolane.
柠檬酸 /柠檬酸铵缓冲液中， 柠檬酸和柠檬酸铵的含量为质量百分比 5wt%, 柠檬酸和柠檬酸铵的含量比为 10: 1。  In the citric acid/ammonium citrate buffer solution, the content of citric acid and ammonium citrate is 5% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
实施例 2 Example 2
56wt%柠檬酸 /柠檬酸四甲铵缓冲水溶液， 1^%聚乙烯醇均聚物 （分子 量 2000)，
Figure imgf000007_0001
氟化氢， lwt%2-膦酸丁垸 -1， 2， 4-三羧酸和 40wt%二甲基亚砜。 56wt% citric acid/tetramethylammonium citrate buffered water solution, 1%% polyvinyl alcohol homopolymer (molecular weight 2000),
Figure imgf000007_0001
Hydrogen fluoride, lwt% 2-butyric acid phosphonium-1, 2,4-tricarboxylic acid and 40% by weight dimethyl sulfoxide.
柠檬酸 /柠檬酸四甲铵缓冲液中，柠檬酸和柠檬酸四甲铵的含量为质量百 分比 60wt%， 柠檬酸和柠檬酸四甲铵的含量比为 1 : 1。  In the citric acid/tetramethylammonium citrate buffer, the content of citric acid and tetramethylammonium citrate is 60% by mass, and the content ratio of citric acid to tetramethylammonium citrate is 1:1.
实施例 3 Example 3
15wt%柠檬酸 /柠檬酸四乙铵缓冲水溶液， lwt%聚乙烯醇共聚物 （分子 量 3000)， lwt%季戊四醇， 2wt%氟化四甲铵， lwt%氨基三亚甲基膦酸和 80wt% N-甲基吡咯垸酮 (NMP)。  15wt% citric acid/tetraethylammonium citrate buffered water solution, lwt% polyvinyl alcohol copolymer (molecular weight 3000), lwt% pentaerythritol, 2wt% tetramethylammonium fluoride, lwt% aminotrimethylenephosphonic acid and 80wt% N- Methylpyrrolidone (NMP).
柠檬酸 /柠檬酸四乙铵缓冲液中，柠檬酸和柠檬酸四乙铵的含量为质量百 分比 10wt%， 柠檬酸和柠檬酸四乙铰的含量比为 1 : 30。 实施例 4 In the citric acid/tetraethylammonium citrate buffer, the content of citric acid and tetraethylammonium citrate is 10% by mass, and the content ratio of citric acid to citric acid tetraethylene hinge is 1:30. Example 4
15wt%柠檬酸 /柠檬酸钾缓冲水溶液， 10^%含羧基聚乙基醚 （分子量 1000) )， 10wt%乙二醇， 0.01wt%氟化四乙铵， lwt%l，3- (羟乙基） -2,4,6- 三膦酸和 63.99wt%l，3-二甲基 -2-咪唑啉酮 （DMI)。  15wt% citric acid/potassium citrate buffered water solution, 10%% carboxyl group-containing polyethyl ether (molecular weight 1000)), 10wt% ethylene glycol, 0.01wt% tetraethylammonium fluoride, lwt%l, 3-(hydroxyl Base) -2,4,6-triphosphonic acid and 63.99 wt% l,3-dimethyl-2-imidazolidinone (DMI).
柠檬酸 /柠檬酸钾缓冲液中， 柠檬酸和柠檬酸钾的含量为质量百分比 50wt%, 柠檬酸和柠檬酸钾的含量比为 10: 1。  In the citric acid/potassium citrate buffer solution, the content of citric acid and potassium citrate is 50% by mass, and the content ratio of citric acid to potassium citrate is 10:1.
实施例 5 Example 5
30wt%柠檬酸 /柠檬酸钠缓冲水溶液， 3^%含羟基聚乙基醚 （分子量 1000)， 2wt%含羧基聚乙醚（分子量 1000)， 0.0001 ％乙二醇， 0.5wt%氟化 氢， 0.5 ％氟化四甲铵，. 1^%乙酸酐和 62.9999wt%2-咪唑垸酮。  30wt% citric acid/sodium citrate buffered water solution, 3%% hydroxyl-containing polyethyl ether (molecular weight 1000), 2wt% carboxyl group-containing polyether (molecular weight 1000), 0.0001% ethylene glycol, 0.5wt% hydrogen fluoride, 0.5% fluorine Tetramethylammonium, 1% acetic anhydride and 62.9999 wt% 2-imidazolium.
柠檬酸 /柠檬酸钠缓冲液中， 柠檬酸和柠檬酸钠的含量为质量百分比 20wt%, 柠檬酸和柠檬酸钠的含量比为 20: 1。  In the citric acid/sodium citrate buffer, the content of citric acid and sodium citrate is 20% by mass, and the ratio of citric acid to sodium citrate is 20:1.
实施例 6 Example 6
40wt%柠檬酸 /柠檬酸铵缓冲水溶液， 0.001wt%聚马来酸酐 （分子量 600)， lwt%乙二醇， lwt%N(CH2OH)3HF， 1^%氟化氢， lwt%没食子酸丙 酯和 55.999wt%甲乙基亚砜。 40wt% citric acid/ammonium citrate buffered water solution, 0.001wt% polymaleic anhydride (molecular weight 600), lwt% ethylene glycol, lwt% N(CH 2 OH) 3 HF, 1^% hydrogen fluoride, lwt% gallic acid Ester and 55.999 wt% methyl ethyl sulfoxide.
柠檬酸 /柠檬酸铵缓冲液中， 柠檬酸和柠檬酸铵的含量为质量百分比 40wt%, 柠檬酸和柠檬酸铵的含量比为 10: 1。  In the citric acid/ammonium citrate buffer solution, the content of citric acid and ammonium citrate is 40% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
实施例 7 Example 7
50wt%柠檬酸 /柠檬酸铵缓冲水溶液， 0.01^%聚丙烯酸 （分子量 700), 0.001^%乙二醇， 2wt%氟化氢， 5wt%邻苯二甲酸甲酯和 42.989wt%l，3-二 甲基 -2-咪唑垸酮。 柠檬酸 /柠檬酸铵缓冲液中， 柠檬酸和柠檬酸铵的含量为质量百分比50wt% citric acid/ammonium citrate buffered water solution, 0.01% polyacrylic acid (molecular weight 700), 0.001% by weight of ethylene glycol, 2wt% hydrogen fluoride, 5wt% methyl phthalate and 42.989wt% l, 3-dimethyl Base-2-imidazolium. In citric acid/ammonium citrate buffer, the content of citric acid and ammonium citrate is mass percentage
15wt%, 柠檬酸和柠檬酸铵的含量比为 25: 1。 15wt%, the content ratio of citric acid to ammonium citrate is 25:1.
实施例 8 Example 8
20wt%柠檬酸 /柠檬酸铵缓冲水溶液， 0.1wt%聚甲基丙烯酸 （分子量 700), 0.01^%乙二醇， 2.5 ％氟化铵， 8wt%对氨基苯甲酸甲酯和 69.39wt% 二甲基甲酰胺。  20wt% citric acid/ammonium citrate buffered water solution, 0.1wt% polymethacrylic acid (molecular weight 700), 0.01^% ethylene glycol, 2.5% ammonium fluoride, 8wt% methylparaben and 69.39wt% dimethyl Carboxamide.
柠檬酸 /柠檬酸铵缓冲液中， 柠檬酸和柠檬酸铵的含量为质量百分比 25wt%, 柠檬酸和柠檬酸铵的含量比为 10: 1。  In the citric acid/ammonium citrate buffer solution, the content of citric acid and ammonium citrate is 25 wt% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
实施例 9 Example 9
25wt%柠檬酸 /柠檬酸铵缓冲水溶液， 0.1^%丙烯酸与马来酸共聚物（分 子量 1000)， 0.1wt%乙二醇， 0.1^%氟化氢， 0.1 ％氟化铵， 0.6wt%氟化四 甲基铵， 2wt%没食子酸和 72^%乙二醇单乙醚。  25wt% citric acid/ammonium citrate buffered water solution, 0.1%% acrylic acid copolymer with maleic acid (molecular weight 1000), 0.1wt% ethylene glycol, 0.1% hydrogen fluoride, 0.1% ammonium fluoride, 0.6wt% fluorinated four Methylammonium, 2% by weight gallic acid and 72% by weight of ethylene glycol monoethyl ether.
柠檬酸 /柠檬酸铵缓冲液中， 柠檬酸和柠檬酸铵的含量为质量百分比 35wt%, 柠檬酸和柠檬酸铵的含量比为 10: 1。  In the citric acid/ammonium citrate buffer solution, the content of citric acid and ammonium citrate is 35 wt% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
实施例 10 Example 10
30wt%柠檬酸 /柠檬酸铵缓冲水溶液， 1^%苯乙烯与丙烯酸共聚物 （分 子量 1500)， 4^%乙二醇， 4wt%丙三醇， 1^%氟化氢， 5wt%邻苯二甲酸， 30wt%l，3-二甲基 -2-咪唑啉酮和 25wt%二丙二醇单丁醚。  30wt% citric acid/ammonium citrate buffered aqueous solution, 1% styrene and acrylic acid copolymer (molecular weight 1500), 4% glycol, 4wt% glycerol, 1% hydrogen fluoride, 5wt% phthalic acid, 30 wt% l,3-dimethyl-2-imidazolidinone and 25 wt% dipropylene glycol monobutyl ether.
柠檬酸 /柠檬酸铵缓冲液中， 柠檬酸和柠檬酸铵的含量为质量百分比 45wt%, 柠檬酸和柠檬酸铵的含量比为 10: 1。  In the citric acid/ammonium citrate buffer solution, the content of citric acid and ammonium citrate is 45 wt% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
实施例 11 Example 11
40wt%柠檬酸 /柠檬酸铵缓冲水溶液， 2wt%苯乙烯与马来酸共聚物 （分 子量 1500)， 2^%乙二醇， lwt%氟化铵和 5wt%环丁砜， 2wt%对氨基苯甲 酸和 48^%丙二醇单丁醚。 40wt% citric acid/ammonium citrate buffered water solution, 2wt% styrene and maleic acid copolymer (minutes Amount 1500), 2% by weight of ethylene glycol, 1% by weight of ammonium fluoride and 5 wt% of sulfolane, 2% by weight of p-aminobenzoic acid and 48% by weight of propylene glycol monobutyl ether.
柠檬酸 /柠檬酸铵缓冲液中， 柠檬酸和柠檬酸铵的含量为质量百分比 5wt%, 柠檬酸和柠檬酸铵的含量比为 10: 1。  In the citric acid/ammonium citrate buffer solution, the content of citric acid and ammonium citrate is 5% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
实施例 12 Example 12
56wt%柠檬酸 /柠檬酸铵缓冲水溶液， 0.5^%丙烯腈与马来酸共聚物（分 子量 1000)， 0.5 ％聚丙烯酸（分子量 700)， 0.5 ％乙二醇， 0.1\^%氟化氢， 0.4^%苯甲酸和 42wt%二乙二醇单甲醚。  56wt% citric acid/ammonium citrate buffered water solution, 0.5% acrylonitrile copolymer with maleic acid (molecular weight 1000), 0.5% polyacrylic acid (molecular weight 700), 0.5% ethylene glycol, 0.1% hydrogen fluoride, 0.4^ % benzoic acid and 42% by weight of diethylene glycol monomethyl ether.
柠檬酸 /柠檬酸铵缓冲液中， 柠檬酸和柠檬酸铵的含量为质量百分比 55wt%, 柠檬酸和柠檬酸铵的含量比为 10: 1。  In the citric acid/ammonium citrate buffer solution, the content of citric acid and ammonium citrate is 55 wt% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
实施例 13 Example 13
20wt%柠檬酸 /柠檬酸铵缓冲水溶液， 0.5^%丙烯酸与马来酸共聚物（分 子量 1000)， 2.5wt%乙二醇， 3^%氟化铵， 4wt%连苯三酚和 70wt%二丙二 醇单甲醚。  20wt% citric acid/ammonium citrate buffered water solution, 0.5%% acrylic acid copolymer with maleic acid (molecular weight 1000), 2.5wt% ethylene glycol, 3^% ammonium fluoride, 4wt% pyrogallol and 70wt% two Propylene glycol monomethyl ether.
柠檬酸 /柠檬酸铵缓冲液中， 柠檬酸和柠檬酸铵的含量为质量百分比 15wt%, 柠檬酸和柠檬酸铵的含量比为 10: 1。  In the citric acid/ammonium citrate buffer solution, the content of citric acid and ammonium citrate is 15% by mass, and the content ratio of citric acid to ammonium citrate is 10:1.
实施例 14 Example 14
30wt%柠檬酸 /柠檬酸铵缓冲水溶液， 0.001^%聚甲基丙烯酸铵（分子量 1000)， 0.008^%乙二醇， 0.1^%氟化氢， 0.891wt%对羟基苯酚和 69wt%l，3- 二乙基 -2-咪唑烷酮。  30wt% citric acid/ammonium citrate buffered water solution, 0.001% polyammonium methacrylate (molecular weight 1000), 0.008^% ethylene glycol, 0.1% hydrogen fluoride, 0.891wt% p-hydroxyphenol and 69wt% l, 3- Ethyl-2-imidazolidinone.
柠檬酸 /柠檬酸铵缓冲液中， 柠檬酸和柠檬酸铵的含量为质量百分比 25wt%, 柠檬酸和柠檬酸铵的含量比为 10: 1 实施例 15 In the citric acid/ammonium citrate buffer solution, the content of citric acid and ammonium citrate is 25 wt% by mass, and the content ratio of citric acid to ammonium citrate is 10:1. Example 15
15wt%柠檬酸 /柠檬酸钠缓冲水溶液， 0.1^%丙烯酸与马来酸共聚物（分 子量 1000)， 0.1wt%聚丙烯酸钾（分子量 1000)，
Figure imgf000011_0001
氟化铵， 5wt%l;2-二羟基苯酚， 5wt%2-膦酸丁垸 -1， 2， 4-三羧酸甲酯和 66.8wt %二 丙二醇单乙醚。 15wt% citric acid/sodium citrate buffered water solution, 0.1%% acrylic acid copolymer with maleic acid (molecular weight 1000), 0.1wt% potassium polyacrylate (molecular weight 1000),
Figure imgf000011_0001
Ammonium fluoride, 5 wt%; 2-dihydroxyphenol, 5 wt% methyl 2-butyrate phosphonium-1,2,4-tricarboxylate and 66.8 wt% dipropylene glycol monoethyl ether.
柠檬酸 /柠檬酸钠缓冲液中， 柠檬酸和柠檬酸钠的含量为质量百分比 10wt%, 柠檬酸和柠檬酸铵的含量比为 20: 1。  In the citric acid/sodium citrate buffer, the content of citric acid and sodium citrate is 10% by mass, and the content ratio of citric acid to ammonium citrate is 20:1.
实施例 16 Example 16
15wt%柠檬酸 /柠檬酸铵缓冲水溶液， 2wt%含羟基聚醚， 0.1wt%聚丙烯 酸钠， 2wt%乙二醇，
Figure imgf000011_0002
二乙 二醇单丁醚。 15wt% citric acid/ammonium citrate buffered water solution, 2wt% hydroxyl-containing polyether, 0.1wt% sodium polyacrylate, 2wt% ethylene glycol,
Figure imgf000011_0002
Diethylene glycol monobutyl ether.
柠檬酸 /柠檬酸铵缓冲液中， 柠檬酸和柠檬酸铵的含量为质量百分比 5wt%, 柠檬酸和柠檬酸铵的含量比为 20: 1。  In the citric acid/ammonium citrate buffer solution, the content of citric acid and ammonium citrate is 5% by mass, and the content ratio of citric acid to ammonium citrate is 20:1.
效果实施例 Effect embodiment
清洗剂 1 24.55wt%柠檬酸 /柠檬酸四甲基铵缓冲水溶液 （22.09wt%水、 2.37wt%柠檬酸四甲基铵和 0.09wt%柠檬酸）， 0.15^%含羟棊聚乙基醚 （分 子量 1000)， 0.3wt%苯并三氮唑， 0.5 ％乙二醇， 1.5^%氟化铰和 73wt%N- 甲基吡咯垸酮。 Cleaning agent 1 24.55wt% citric acid / tetramethylammonium citrate buffered water solution (22.09wt% water, 2.37wt% tetramethylammonium citrate and 0.09wt% citric acid), 0.15%% hydroxyindole polyethyl ether (molecular weight 1000), 0.3 wt% benzotriazole, 0.5% ethylene glycol, 1.5%% fluorinated hinge and 73 wt% N-methylpyrrolidone.
清洗剂 2 24.55wt%柠檬酸 /柠檬酸四乙基铵缓冲水溶液 （22.09wt%水、 2.37wt%柠檬酸四乙基铵和 0.09wt%柠檬酸）， 0.15^%含羟基聚乙基醚 （分 子量 1000)， 0.3wt%4-羧基苯并三氮唑， 0.5wt%乙二醇，
Figure imgf000011_0003
10wt% 1， 3-二甲基 -2-咪唑啉酮和 63wt% N_甲基吡咯垸酮。 清洗剂 3 34.55wt%柠檬酸 /柠檬酸四乙基铵缓冲水溶液 （31.09wt%水、 3.33wt%柠檬酸四乙基铵盐和 0.13wt%柠檬酸）， 0.15^/。含羟基聚乙基醚（分 子量 L000 ) , 0.3wt%甲基苯并三氮唑， 0.5wt%乙二醇， 1 .5^%氟化铵和 63wt%N-甲基吡咯垸酮。 Cleaning agent 2 24.55wt% citric acid / tetraethylammonium citrate buffered aqueous solution (22.09wt% water, 2.37wt% tetraethylammonium citrate and 0.09wt% citric acid), 0.15%% hydroxyl-containing polyethyl ether ( Molecular weight 1000), 0.3wt% 4-carboxybenzotriazole, 0.5wt% ethylene glycol,
Figure imgf000011_0003
10 wt% 1, 3-dimethyl-2-imidazolidinone and 63 wt% N-methylpyrrolidone. Cleaning agent 3 34.55 wt% citric acid / tetraethylammonium citrate buffered aqueous solution (31.09 wt% water, 3.33 wt% tetraethylammonium citrate and 0.13 wt% citric acid), 0.15 ^ /. Hydroxy-containing polyethyl ether (molecular weight L000), 0.3 wt% methylbenzotriazole, 0.5 wt% ethylene glycol, 1.5% ammonium fluoride and 63 wt% N-methylpyrrolidone.
按下述方法对清洗剂 1~3进行对金属和非金属腐蚀速率的测试，测试结 果如表 1所示。  The cleaning agents 1 to 3 were tested for metal and non-metal corrosion rates as follows. The test results are shown in Table 1.
1. 溶液的金属腐蚀速率测试方法：  1. Test method for metal corrosion rate of solution:
. 1 )利用 Napson四点探针仪测试 4*4cm铝空白硅片的电阻初值 （Rsl );  1) Using a Napson four-point prober to test the initial resistance value (Rsl) of a 4*4 cm aluminum blank silicon wafer;
2) 将该 4*4cm铝空白硅片浸泡在预先己经恒温到 35°C的溶液中 30分 钟；  2) immersing the 4*4 cm aluminum blank silicon wafer in a solution which has been previously thermostated to 35 ° C for 30 minutes;
3 ) 取出该 4*4cm铝空白硅片， 用去离子水清洗， 高纯氮气吹干， 再利 用 Napson四点探针仪测试 4*4cm铝空白硅片的电阻值 （Rs2);  3) Remove the 4*4cm aluminum blank silicon wafer, wash it with deionized water, dry it with high purity nitrogen, and test the resistance value (Rs2) of 4*4cm aluminum blank silicon wafer by Napson four-point probe instrument;
4) 重复第二和第三步再测试一次， 电阻值记为 Rs3;  4) Repeat the second and third steps and test again, the resistance value is recorded as Rs3;
5 ) 把上述电阻值和浸泡时间输入到合适的程序可计算出其腐蚀速率。 5) Enter the resistance value and soak time into the appropriate program to calculate the corrosion rate.
2. 溶液的非金属腐蚀速率测试方法： 2. Test method for non-metallic corrosion rate of solution:
1 ) 利用 Nanospec6100测厚仪测试 4*4cm PETEOS硅片的厚度 （T1 ); 1) Test the thickness of the 4*4cm PETEOS wafer (T1) using the Nanospec6100 thickness gauge;
2)将该 4*4cmPETEOS硅片浸泡在预先已经恒温到 35°C的溶液中 30分 钟； 2) immersing the 4*4 cm PETEOS silicon wafer in a solution which has been previously thermostated to 35 ° C for 30 minutes;
3 ) 取出该 4*4cmPETEOS硅片， 用去离子水清洗， 高纯氮气吹干， 再 利用 Nanospec6100测厚仪测试 4*4cmPETEOS硅片的厚度 （T2);  3) Remove the 4*4cm PETEOS wafer, wash it with deionized water, dry it with high purity nitrogen, and test the thickness of the 4*4cm PETEOS wafer (T2) with a Nanospec6100 thickness gauge;
4) 重复第二和第三步再测试一次厚度记为 T3 ;  4) Repeat the second and third steps and test the thickness again as T3;
5 ) 把上述厚度值和浸泡时间输入到合适的程序可计算出其腐蚀速率。 表 1 清洗剂 1〜3腐蚀速率测试结果 5) Enter the above thickness value and soak time into the appropriate program to calculate the corrosion rate. Table 1 Cleaning agent 1~3 corrosion rate test results
Figure imgf000013_0001
Figure imgf000013_0001
从表 1中可以看出： 本发明的清洗液组合物对半导体制成中所用的金属 (如金属铝） 和非金属 （如 PETEOS) 的腐蚀速率均接近或小于半导体业界 通常所要求的 2埃每分钟， 基本不会侵蚀基材。  It can be seen from Table 1 that the cleaning liquid composition of the present invention has a corrosion rate for metals (such as metal aluminum) and non-metal (such as PETEOS) used in semiconductor fabrication, which are close to or less than 2 angstroms normally required by the semiconductor industry. Every minute, it does not substantially erode the substrate.
用表 1中的溶液对等离子刻蚀残留物进行清洗发现，其等离子刻蚀残留 物均被去除， 而且基本没有腐蚀金属和非金属。  Cleaning the plasma etch residue with the solution in Table 1 revealed that the plasma etch residue was removed and substantially no corrosion of metals and non-metals.

Claims

权利要求 Rights request
1.一种清洗等离子刻蚀残留物的清洗液，其特征在于含有：柠檬酸 /柠檬 酸盐缓冲水溶液、 高分子腐蚀抑制剂、 抗冻剂、 氟化物和溶剂。 A cleaning liquid for cleaning a plasma etching residue, comprising: a citric acid/citrate buffer aqueous solution, a polymer corrosion inhibitor, a cryoprotectant, a fluoride, and a solvent.
2.如权利要求 1所述的清洗液，其特征在于：所述的柠檬酸 /柠檬酸盐缓 冲水溶液在清洗液中的含量为质量百分比 15%〜56%。  The cleaning solution according to claim 1, wherein the citric acid/citrate buffer aqueous solution is contained in the cleaning solution in an amount of 15% to 56% by mass.
3.如权利要求 1所述的清洗液， 其特征在于： 所述的柠檬酸盐为柠檬酸 与无机碱或季胺氢氧化物形成的盐。  The cleaning solution according to claim 1, wherein the citrate is a salt of citric acid and an inorganic or quaternary ammonium hydroxide.
4.如权利要求 3所述的清洗液， 其特征在于： 所述的无机碱为氨水或氢 氧化钾； 所述的季胺氢氧化物为四甲基氢氧化铵或四乙基氢氧化铵。  The cleaning solution according to claim 3, wherein: the inorganic base is ammonia water or potassium hydroxide; and the quaternary ammonium hydroxide is tetramethylammonium hydroxide or tetraethylammonium hydroxide. .
5.如权利要求 1所述的清洗液，其特征在于：所述的柠檬酸 /柠檬酸盐缓 冲水溶液中柠檬酸和柠檬酸盐的含量为质量百分比 5%〜60%。  The cleaning solution according to claim 1, wherein the citric acid/citrate buffer aqueous solution has a citric acid and citrate content of 5% to 60% by mass.
6.如权利要求 5所述的清洗液，其特征在于：所述的柠檬酸 /柠檬酸盐缓 冲水溶液中柠檬酸和柠檬酸盐的含量为质量百分比 10%〜50%。  The cleaning solution according to claim 5, wherein the citric acid/citrate buffer aqueous solution has a citric acid and citrate content of 10% to 50% by mass.
7.如权利要求 1所述的清洗液， 其特征在于： 所述的高分子腐蚀抑制剂 或抗冻剂的含量为质量百分比 0.0001%〜10%。  The cleaning solution according to claim 1, wherein the content of the polymer corrosion inhibitor or the antifreezing agent is 0.0001% to 10% by mass.
8.如权利要求 1所述的清洗液， 其特征在于： 所述的抗冻剂为多元醇中 的一种或多种。  The cleaning solution according to claim 1, wherein the antifreezing agent is one or more of a polyhydric alcohol.
9.如权利要求 8所述的清洗液， 其特征在于： 所述的多元醇为乙二醇、 丙三醇或季戊四醇。  The cleaning solution according to claim 8, wherein the polyol is ethylene glycol, glycerol or pentaerythritol.
10.如权利要求 1所述的清洗液，其特征在于：所述的高分子腐蚀抑制剂 为含羟基聚合物和含羧基聚合物中的一种或多种。  The cleaning solution according to claim 1, wherein said polymer corrosion inhibitor is one or more of a hydroxyl group-containing polymer and a carboxyl group-containing polymer.
11.如权利要求 10所述的清洗液， 其特征在于： 所述的含羟基聚合物为 含羟基聚醚或聚乙烯醇； 所述的含羧基聚合物为含羧基聚醚、 聚马来酸酐、 聚丙烯酸、聚甲基丙烯酸、丙烯酸与马来酸共聚物、苯乙烯与丙烯酸共聚物、 苯乙烯与马来酸共聚物、 丙烯腈与马来酸共聚物或上述化合物的铰盐、钾盐 或钠盐。 The cleaning solution according to claim 10, wherein: the hydroxyl group-containing polymer is a hydroxyl group-containing polyether or polyvinyl alcohol; and the carboxyl group-containing polymer is a carboxyl group-containing polyether or polymaleic anhydride. , polyacrylic acid, polymethacrylic acid, copolymer of acrylic acid and maleic acid, copolymer of styrene and acrylic acid, copolymer of styrene and maleic acid, copolymer of acrylonitrile and maleic acid or hinge salt or potassium salt of the above compound Or sodium salt.
12.如权利要求 1所述的清洗液，其特征在于：所述的氟化物的含量为质 量百分比 0.01%〜3%。 The cleaning solution according to claim 1, wherein the fluoride is contained in an amount of 0.01% to 3% by mass.
B.如权利要求 1所述的清洗液，其特征在于：所述的氟化物为氟化氢和 氟化氢与碱形成的盐中的一种或多种。  B. The cleaning solution according to claim 1, wherein the fluoride is one or more of hydrogen fluoride and a salt of hydrogen fluoride and a base.
14.如权利要求 13所述的清洗液， 其特征在于： 所述的碱为氨水、 季胺 氢氧化物或醇胺。  The cleaning solution according to claim 13, wherein the base is ammonia water, quaternary ammonium hydroxide or alcohol amine.
15.如权利要求 1所述的清洗液，其特征在于：所述的溶剂的含量为质量 百分比 40%〜80%。  The cleaning solution according to claim 1, wherein the solvent is contained in an amount of 40% to 80% by mass.
16.如权利要求 1所述的清洗液， 其特征在于： 所述的溶剂为亚砜、 砜、 咪唑垸酮、 吡咯垸酮、 咪唑啉酮、 酰胺和醚中的一种或多种。  The cleaning solution according to claim 1, wherein the solvent is one or more of sulfoxide, sulfone, imidazolium, pyrrolidone, imidazolidinone, amide and ether.
17.如权利要求 16所述的清洗液， 其特征在于： 所述的亚砜为二甲基亚. 砜、 二乙基亚砜或甲乙基亚砜； 所述的砜为甲基砜、 乙基砜或环丁砜； 所述 的咪唑垸酮为 2-咪唑烷酮、 1,3-二甲基 -2-咪唑垸酮或 1，3-二乙基 -2-咪唑垸酮;. 所述的吡咯垸酮为 N-甲基吡咯垸酮； 所述的咪唑啉酮为 1,3-二甲基 -2-咪唑 啉酮； 所述的酰胺为二甲基甲酰胺； 所述的醚为乙二醇单甲醚、 乙二醇单乙 醚、 乙二醇单丁醚、 二乙二醇单甲醚、 二乙二醇单乙醚、 二乙二醇单丁醚、 丙二醇单甲醚、 丙二醇单乙醚、 丙二醇单丁醚、 二丙二醇单甲醚、 二丙二醇 单乙醚或二丙二醇单丁醚。 .  The cleaning solution according to claim 16, wherein: the sulfoxide is dimethyl sulfoxide, diethyl sulfoxide or methyl sulfoxide; the sulfone is methyl sulfone, and a sulfone or a sulfolane; the imidazolium is 2-imidazolidinone, 1,3-dimethyl-2-imidazolium or 1,3-diethyl-2-imidazolium; Pyrrolidone is N-methylpyrrolidone; said imidazolinone is 1,3-dimethyl-2-imidazolidinone; said amide is dimethylformamide; said ether is B Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or dipropylene glycol monobutyl ether. .
18.如权利要求 1所述的清洗液，其特征在于：所述的清洗液还含有小分 子抑制剂。  18. The cleaning fluid of claim 1 wherein said cleaning fluid further comprises a small molecule inhibitor.
19.如权利要求 18所述的清洗液， 其特征在于： 所述的小分子抑制剂的 含量为小于或等于质量百分比 10%。  The cleaning solution according to claim 18, wherein the content of the small molecule inhibitor is less than or equal to 10% by mass.
20.如权利要求 18所述的清洗液， 其特征在于： 所述的小分子抑制剂选 自酚类、 羧酸类、 羧酸酯类、 酸酐类、 苯并三氮唑类、 膦酸类和膦酸酯类缓 蚀剂中的一种或多种。  The cleaning solution according to claim 18, wherein the small molecule inhibitor is selected from the group consisting of phenols, carboxylic acids, carboxylic acid esters, acid anhydrides, benzotriazoles, and phosphonic acids. And one or more of the phosphonate corrosion inhibitors.
21.如权利要求 20所述的清洗液，其特征在于： 所述的酚类为苯酚、 1，2- 二羟基苯酚、 对羟基苯酚或连苯三酚； 所述的羧酸类为苯甲酸、 对氨基苯甲 酸、 邻苯二甲酸或没食子酸； 所述的羧酸酯类为对氨基苯甲酸甲酯、 邻苯二 甲酸甲酯或没食子酸丙酯； 所述的酸酐类为乙酸酐或己酸酐； 所述的苯并三 氮唑类为苯并三氮唑、 甲基苯并三氮唑或 4-羧基苯并三氮唑； 所述的磷酸类 为 1，3- (羟乙基） -2,4,6-三膦酸、 氨基三亚甲基膦酸或 2-膦酸丁垸 -1， 2， 4- 三羧酸。 The cleaning solution according to claim 20, wherein the phenol is phenol, 1,2-dihydroxyphenol, p-hydroxyphenol or pyrogallol; and the carboxylic acid is benzoic acid. P-aminobenzoic acid Acid, phthalic acid or gallic acid; the carboxylic acid ester is methyl p-aminobenzoate, methyl phthalate or propyl gallate; the acid anhydride is acetic anhydride or hexanoic anhydride; The benzotriazoles are benzotriazole, methylbenzotriazole or 4-carboxybenzotriazole; the phosphoric acid is 1,3-(hydroxyethyl)-2. 4,6-triphosphonic acid, aminotrimethylenephosphonic acid or 2-phosphonic acid butyl phosphonium-1,2,4-tricarboxylic acid.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7901589B2 (en) 2009-06-29 2011-03-08 E.I. Du Pont De Nemours And Company Propanediol soil resist compositions
US8357621B2 (en) 2009-06-29 2013-01-22 E.I. Du Pont De Nemours And Company Soil resist method
EP3588535A1 (en) * 2018-06-26 2020-01-01 Versum Materials US, LLC Post chemical mechanical planarization (cmp) cleaning
CN113501670A (en) * 2021-07-20 2021-10-15 海南海控特玻科技有限公司 Chemical strengthening and film-covering strengthening process for ultrathin high-aluminum glass
CN115404119A (en) * 2022-08-23 2022-11-29 煤炭科学技术研究院有限公司 Hydraulic support antifreeze fluid composite additive and preparation method and application thereof

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101750911A (en) * 2008-11-28 2010-06-23 安集微电子（上海）有限公司 Photoresist detergent composition
CN101955852A (en) * 2009-07-13 2011-01-26 安集微电子（上海）有限公司 Cleaning solution for plasma etching residues
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CN102338994B (en) * 2010-07-23 2014-12-31 安集微电子（上海）有限公司 Cleaning solution for photoresist
CN102399648B (en) * 2010-09-10 2015-04-15 安集微电子（上海）有限公司 Fluorine-containing cleaning solution
CN102533273A (en) * 2010-12-31 2012-07-04 第一毛织株式会社 Cleaning composition for semiconductor device and method of cleaning semiconductor device using the same
CN103103539A (en) * 2012-11-13 2013-05-15 三达奥克化学股份有限公司 Environment-friendly nuclear power equipment cleaning agent
CN103513524A (en) * 2013-09-25 2014-01-15 杨桂望 Semiconductor remover
CN103676504B (en) * 2013-12-13 2016-08-17 江阴润玛电子材料股份有限公司 A kind of aqueous photoresist lift off liquid
CN103980905B (en) * 2014-05-07 2017-04-05 佛山市中山大学研究院 A kind of etching solution and its engraving method and application for oxide material system
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US10301580B2 (en) * 2014-12-30 2019-05-28 Versum Materials Us, Llc Stripping compositions having high WN/W etching selectivity
CN104614954A (en) * 2015-01-09 2015-05-13 苏州瑞红电子化学品有限公司 Photoresist-removing water-based stripping liquid composition
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CN107229192B (en) * 2017-07-25 2019-05-10 上海新阳半导体材料股份有限公司 A kind of fluorine-containing plasma etching residue cleaning, preparation method and application
CN107300839B (en) * 2017-07-25 2019-06-07 上海新阳半导体材料股份有限公司 A kind of fluorine-containing plasma etching residue cleaning, preparation method and application
CN107229194B (en) * 2017-07-25 2019-05-10 上海新阳半导体材料股份有限公司 A kind of fluorine-containing plasma etching residue cleaning, preparation method and application
CN108803262A (en) * 2018-07-03 2018-11-13 昆山欣谷微电子材料有限公司 A kind of acidity photoresist lift off liquid
CN110302489B (en) * 2019-07-22 2021-05-25 北京利新泰奇科技有限公司 Environment-friendly flame-retardant antifreezing water-based extinguishing agent
CN113078209B (en) * 2021-03-24 2022-06-21 长鑫存储技术有限公司 Semiconductor structure, manufacturing method thereof and peripheral circuit

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030181344A1 (en) * 2002-03-12 2003-09-25 Kazuto Ikemoto Photoresist stripping composition and cleaning composition
US20050119143A1 (en) * 1999-01-27 2005-06-02 Egbe Matthew I. Compositions for the removal of organic and inorganic residues
CN1715389A (en) * 2004-07-01 2006-01-04 气体产品与化学公司 Composition for stripping and cleaning and use thereof
CN1900363A (en) * 2005-07-21 2007-01-24 安集微电子（上海）有限公司 Cleaning liquid and its use

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050119143A1 (en) * 1999-01-27 2005-06-02 Egbe Matthew I. Compositions for the removal of organic and inorganic residues
US20030181344A1 (en) * 2002-03-12 2003-09-25 Kazuto Ikemoto Photoresist stripping composition and cleaning composition
CN1715389A (en) * 2004-07-01 2006-01-04 气体产品与化学公司 Composition for stripping and cleaning and use thereof
CN1900363A (en) * 2005-07-21 2007-01-24 安集微电子（上海）有限公司 Cleaning liquid and its use

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7901589B2 (en) 2009-06-29 2011-03-08 E.I. Du Pont De Nemours And Company Propanediol soil resist compositions
US8357621B2 (en) 2009-06-29 2013-01-22 E.I. Du Pont De Nemours And Company Soil resist method
EP3588535A1 (en) * 2018-06-26 2020-01-01 Versum Materials US, LLC Post chemical mechanical planarization (cmp) cleaning
US11560533B2 (en) 2018-06-26 2023-01-24 Versum Materials Us, Llc Post chemical mechanical planarization (CMP) cleaning
CN113501670A (en) * 2021-07-20 2021-10-15 海南海控特玻科技有限公司 Chemical strengthening and film-covering strengthening process for ultrathin high-aluminum glass
CN113501670B (en) * 2021-07-20 2022-05-31 海南海控特玻科技有限公司 Chemical strengthening and film-covering strengthening process for ultrathin high-aluminum glass
CN115404119A (en) * 2022-08-23 2022-11-29 煤炭科学技术研究院有限公司 Hydraulic support antifreeze fluid composite additive and preparation method and application thereof
CN115404119B (en) * 2022-08-23 2023-08-22 煤炭科学技术研究院有限公司 Hydraulic support antifreeze fluid composite additive and preparation method and application thereof

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